EP1384064B1 - Verfahren zur Steuerung der Oxidation von Propen mit H2O2 - Google Patents

Verfahren zur Steuerung der Oxidation von Propen mit H2O2 Download PDF

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Publication number
EP1384064B1
EP1384064B1 EP02722046A EP02722046A EP1384064B1 EP 1384064 B1 EP1384064 B1 EP 1384064B1 EP 02722046 A EP02722046 A EP 02722046A EP 02722046 A EP02722046 A EP 02722046A EP 1384064 B1 EP1384064 B1 EP 1384064B1
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Prior art keywords
hydrogen peroxide
reaction
determination
reagent
synthesis
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German (de)
English (en)
French (fr)
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EP1384064A2 (de
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Thomas Beuermann
Joaquim Henrique Teles
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BASF SE
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BASF SE
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/20—Oxygen containing
    • Y10T436/206664—Ozone or peroxide

Definitions

  • the present invention relates to a process for controlling a process for the oxidation of propene to propylene oxide with hydrogen peroxide in methanolic solution in the presence of a zeolite catalyst which is a titanium silicalite having MFI structure, during which reaction the content of hydrogen peroxide in the reaction mixture is determined online ,
  • the conversion of educts of chemical syntheses is usually determined by their content in the synthesis solution or the synthesis effluent.
  • a particularly important case is formed by oxidation reactions with hydrogen peroxide.
  • hydrogen peroxide can be determined both quantitatively and qualitatively by utilizing its oxidizing and reducing properties.
  • hydrogen peroxide can be detected, for example, by the reaction with a titanium (IV) oxide sulfate solution. Due to the formation of a titanium (IV) peroxy complex occurs while an intense yellowing. The qualitative detection is also the reaction with potassium dichromate solution and dilute sulfuric acid, as a result of which a blue coloration of the reaction solution occurs.
  • the quantitative determination is carried out, for example, by the oximetric titration, which is well known to the person skilled in the art, with the following reagents: potassium permanganate, sodium iodide or cerium (IV) sulfate.
  • further substances are present in the analysis solution.
  • further unreacted starting materials as well as by-products formed in addition to the main product.
  • hydrogen peroxide determination in low concentration hydrogen peroxide or / and complex nature synthesis solutions typically can not be directly performed by measurements such as optical absorption, reflection, or emission, such as fluorescence or phosphorescence.
  • the measurement of the absorption of hydrogen peroxide in the near infrared range for example, the FT-NIR spectroscopy in the range of 4631 to 5140 cm -1 fails , in addition to the reasons mentioned above, also on the interference of water and organic hydroperoxides.
  • the measurement of the absorption of hydrogen peroxide in the ultraviolet range e.g. the measurement of UV absorption at 254 or 280 nm is only suitable for reliably determining the concentration of hydrogen peroxide in water / methanol solutions.
  • organic hydroperoxides are present in the synthesis solution, a reliable analysis of hydrogen peroxide by this method is no longer possible.
  • colorimetric methods are well suited for the selective determination of hydrogen peroxide in synthesis solutions of complex nature and / or low content of hydrogen peroxide.
  • a suitable reagent by reacting the sample to be examined with a suitable reagent, a substance is produced which absorbs or fluoresces in the UV / VIS region of the spectrum and is thus determinable.
  • This reaction is catalyzed by a peroxidase (eg radish peroxidase type II, EC No.
  • titanium sulfate method is suitable for the quantitative colorimetric determination of hydrogen peroxide in the presence of organic hydroperoxides. This evidence is negatively affected only by hydroperoxides which tend to cleave hydrogen peroxide in an acidic medium (eg hemiperacetals).
  • This method is based on the yellow-colored titanyl peroxo complex formed by the reaction of existing hydrogen peroxide with a titanium (IV) reagent (for example, titanyl sulfate, titanium (IV) chloride or potassium titanyl oxalate). This has a strong absorption at about 408 nm. Details on how to perform this method For example, the literature can be found at Kaká , Z.
  • a third colorimetric and also suitable for the selective determination of hydrogen peroxide method is the so-called "cobalt-bicarbonate method". This is based on the reaction of hydrogen peroxide with Co (II) ions to form a colored cobalt-peroxo complex. This absorbs very strongly at about 260 nm.
  • This method can be found in the literature known to the person skilled in the art, for example in Masschelen, W. "Spectrophotometric Determination of Residual Hydrogen Peroxide", Water and Sewerage Works, p. 69, August 1977 ,
  • the sensitivity of this method is very high, so that, for example, hydrogen peroxide concentrations of about 0.02 ppm can be detected.
  • certain compounds which, for example, are formed as by-products of the oxidation of propylene with hydrogen peroxide eg acetone, with cut-off at a wavelength of ⁇ c ⁇ 330 nm
  • acetone with cut-off at a wavelength of ⁇ c ⁇ 330 nm
  • an analysis method whose end point can be indexed photometrically can also be carried out by means of automated analysis devices.
  • Their use in the context of a synthesis process was previously often separated from the data processing system used for evaluation or process control and is, if at all, only indirectly coupled with this, so to speak "offline”.
  • the synthesis conditions can not be adapted fast enough to the changed content of hydrogen peroxide.
  • the synthesis is not optimal for this period until adaptation. During this time, for example, more unwanted by-products may arise. These in turn reduce the yield of the actual product and make it difficult to work up.
  • an on-line determination of the hydrogen peroxide content would be if the oxidation reaction is carried out continuously in the presence of a catalyst whose catalytic activity is not constant (e.g., due to deactivation of the catalyst). In this case, in order to maintain a predetermined set point for the residual hydrogen peroxide content, it is necessary to constantly adjust the reaction conditions to compensate for the changing catalytic activity.
  • on-line determination of the content of hydrogen peroxide as used in the context of the present invention, the described under device or device arrangements of suitable for the determination of hydrogen peroxide devices, which in a direct manner with at least one data processing system and through which it is possible to intervene to intervene in a synthesis process.
  • a preferred device for "determining the content of hydrogen peroxide in the context of this invention is described in US Pat DE 101 211 94.5 the applicant described.
  • a device in communication with at least one data processing system.
  • This connection can be made, for example, by further devices known to the person skilled in the art. These are capable of, for example, receiving, amplifying, converting or otherwise modulating the signals originating from the device arrangement for determination. Furthermore, they can be connected to each other as well as to the device arrangement for the determination as well as to the at least one data processing system via commercially available cable connections, infrared interfaces or similar means suitable for the transmission of signals.
  • the device arrangement for the online determination of hydrogen peroxide comprises at least one sampling device for taking a sample from the reaction mixture obtained in the course of the synthesis, at least one device arrangement for processing the sample and at least one Device which is suitable for determining the specific absorption of the sample in a suitable wavelength range.
  • the device arrangement in question comprises at least one device which is connected to the devices just mentioned and which is suitable for taking over the control function of the individual devices so as to coordinate their operation.
  • the data determined by the device arrangement for the online determination of hydrogen peroxide are evaluated via at least one data processing system connected to this device arrangement and converted into control commands for the process control of the synthesis plant. These control commands will then be forwarded to the process control of the synthesis system (process control system) which is connected to the at least one data processing system.
  • a mixture typically used in the present process comprises at least the products resulting from the reaction in question here, intermediates, by-products and educts, such as hydrogen peroxide.
  • Chemical reactions which produce the mixture obtained for the determination of hydrogen peroxide with the aid of the process according to the invention can be all chemical reactions known to the person skilled in the art, in which hydrogen peroxide is used, for example, as starting material or can also be formed as by-product or intermediate product.
  • the resulting mixture is first admixed with at least one reagent which forms a substance which can be detected by optical methods using hydrogen peroxide.
  • Reagents with the abovementioned property are in principle all compounds known to the person skilled in the art for this purpose. They can be used individually or in a mixture with each other or together with other compounds.
  • Other compounds may, for example, stabilizing or solvent additives.
  • the formation of the substance relies on the reagent to form a complex or compound with hydrogen peroxide which can be detected by optical methods.
  • the content of the substance and thus the content of hydrogen peroxide can be determined in comparison with a respectively suitable standard.
  • the at least one reagent is selected from the group consisting of metals of IV. To IX. Subgroup of the Periodic Table of the Elements.
  • the at least one reagent is selected from the group consisting of titanium, cobalt, chromium, zirconium, hafnium, vanadium, niobium or tantalum-containing compounds.
  • titanium (IV) compounds such as titanyl sulfate, cobalt (II) salts, for example cobalt (II) sulfate or cobalt bicarbonate, molybdenum (VI) salts, for example ammonium molybdate, vanadium salts such as vanadyl sulfate, etc ,
  • Titanium sulfate or cobalt (II) sulfate is particularly preferably used as the reagent.
  • the at least one reagent comprises a leuco dye and a peroxidase.
  • leuco dye is understood to mean any dye whose oxidized form has a weaker or stronger or different specific absorption in the optical spectrum, eg shifted with respect to the absorption wavelength, than its reduced form.
  • leuco crystal violet tris (- 4-dimethylaminophenyl) methane
  • leucomalachite green bis (- 4-dimethylaminophenyl) -phenylmethane
  • o-dianisidine e.g. 10-methyl- ⁇ - (p-formylphenyl) -acridinium carboxylate and purpurogallin used.
  • Leuco crystal violet tris (- 4-dimethylaminophenyl) methane
  • purpurogallin is particularly preferably used.
  • the formation of a detectable by optical methods substance proceeds in the reaction of hydrogen peroxide with the respective Leuco dye via an electron transfer reaction, which is catalyzed by a peroxidase.
  • the leuco dye is oxidized.
  • the oxidized form of the leuco dye then absorbs at a specific wavelength and can thus be detected by optical methods. Again, the content of oxidized leuco-dye and thus the content of hydrogen peroxide can be determined by comparison with a suitable standard.
  • the substance resulting from the reaction of hydrogen peroxide to be determined with the respective reagent is detected on the basis of its specific absorption in a wavelength range suitable for each of them by means of suitable optical methods.
  • Examples include UV, UV / VIS, VIS, IR, NIR, Raman spectroscopy. In this case, either the absorption (or transmission), the reflection or the fluorescence can be determined.
  • the content of the substance is determined by measuring its specific absorption and / or fluorescence in the UV / VIS region of the spectrum.
  • the devices suitable for detection in the context of the present invention are generally commercially available spectrometers for the respective wavelength range, preferably spectrometers operating in the UV / VIS range.
  • alkene as used in the context of the present invention, all compounds are understood to have at least one C-C double bond.
  • the hydrogen peroxide used for the reaction with propene in the context of the invention can be prepared, for example, with the aid of the anthraquinone process, after which virtually the entire amount of the hydrogen peroxide produced worldwide is produced.
  • This method is based on the catalytic hydrogenation of an anthraquinone compound to the corresponding anthrahydroquinone compound, followed by reaction thereof with oxygen to form hydrogen peroxide and subsequent separation of the hydrogen peroxide formed by extraction.
  • the catalytic cycle is closed by rehydrogenation of the rebuilt anthraquinone compound.
  • At least one salt contained in the hydrogen peroxide solution may be removed by means of an ion exchange device from the hydrogen peroxide solution, characterized in that the device comprises at least one non-acidic ion exchange bed having a flow cross-sectional area F and a height H wherein the height H of the ion exchange bed is less than or equal to 2.5 • F 1/2 and in particular less than or equal to 1.5 • F 1/2 .
  • the device comprises at least one non-acidic ion exchange bed having a flow cross-sectional area F and a height H wherein the height H of the ion exchange bed is less than or equal to 2.5 • F 1/2 and in particular less than or equal to 1.5 • F 1/2 .
  • all non-acidic ion exchange beds with cation exchangers and / or anion exchangers can be used in the context of the present invention. Even within an ion exchange bed, cation and anion exchangers can be used as so-called mixed beds.
  • non-acid ion exchangers only one type of non-acid ion exchangers is used. Further preferred is the use of a basic ion exchanger, particularly preferably that of a basic anion exchanger and more preferably that of a weakly basic anion exchanger.
  • a zeolite catalyst which is a titanium silicalite unit MFI structure.
  • Zeolites are known to be crystalline aluminosilicates having ordered channel and cage structures that have micropores that are preferably less than about 0.9 nm.
  • the network of such zeolites is composed of SiO 4 and AlO 4 tetrahedra which are linked by common oxygen bridges.
  • An overview of the known structures can be found, for example WM Meier, DH Olson and Ch. Baerlocher, "Atlas of Zeolite Structure Types", Elsevier, 4th ed., London 1996 ,
  • zeolites that contain no aluminum and in which in the silicate lattice in place of the Si (IV) partially titanium as Ti (IV).
  • These titanium zeolites In particular, those having a crystal structure of the MFI type, as well as ways for their preparation are described, for example in the EP-A 0 311 983 or EP-A 405 978 ,
  • silicon and titanium such materials can also contain additional elements such.
  • the titanium of the zeolite may be partially or completely replaced by vanadium, zirconium, chromium or niobium or a mixture of two or more thereof.
  • the molar ratio of titanium and / or vanadium, zirconium, chromium or niobium to the sum of silicon and titanium and / or vanadium and / or zirconium and / or chromium and / or niobium is usually in the range from 0.01: 1 to 0.1: 1.
  • Titanium zeolites in particular those having a crystal structure of the MFI type, as well as possibilities for their preparation, for example in the WO 98/55228 .
  • WO 98/03394 WO 98/03395 .
  • EP-A 0 311 983 or the EP-A 0 405 978 the scope of which is fully incorporated into the context of the present application.
  • Titanium zeolites with MFI structure are known to be identifiable by a particular pattern in determining their X-ray diffraction recordings as well as an infrared (IR) scaffolding band at about 960 cm -1 and thus by alkali metal titanates or crystalline and amorphous TiO 2 Differentiate between phases.
  • IR infrared
  • the present invention also relates to a process as described above, characterized in that the catalyst is a titanium silicalite of structure TS-1 structure.
  • the current synthesis process can be optimally controlled.
  • the determination is carried out in particular in the reaction.
  • the determination is preferably carried out in the reaction either in individual, selected or all reactors.
  • the overall yield, or of each reactor, and the purity of the respective reaction effluent and thus also of the product could be optimized.
  • the safety risk caused by the hydrogen peroxide possibly present in the reaction effluent of a synthesis without optimized control could be minimized.
  • the determination of the content of hydrogen peroxide in the course of the process according to the invention is carried out largely periodically, preferably at a frequency between 0.5 and 100 h -1 . Particularly preferred are frequencies in the range between 1 and 60 h -1 .
  • the temperature increase required for each regulation step was determined by the short-term determination of the hydrogen peroxide content in the respective reaction effluent. Due to the existing online connection between the device arrangement for determining the content of hydrogen peroxide and the process control of the synthesis plant, the respective regulation takes place without significant time delay.
  • the present invention also relates to a method for controlling a process for the oxidation of propene of the type according to the invention, wherein the reaction takes place in several reactors.
  • This is characterized in that in at least one, preferably all reactors, the content of hydrogen peroxide by means of the method according to the invention of the on-line determination of the content of hydrogen peroxide is possible.
  • the inventive method is, as described above, used for the reaction of propene to propylene oxide with hydrogen peroxide in methanolic solution in the presence of a titanium silicalite with MFI structure.
  • propylene is reacted with hydrogen peroxide in the presence of methanol, a basic salt and TS-1 as a catalyst in a first reactor (main reactor, for example a tube-bundle reactor).
  • main reactor for example a tube-bundle reactor
  • reaction pressure is selected and kept constant at a value at which no gas phase is present during the reaction.
  • the temperature is chosen so that the hydrogen peroxide conversion in the discharge of the reactor 85 to 95%, preferably 88 to 93%.
  • the temperature must be continuously adjusted for the reasons mentioned above. In general, the required temperature increase, depending on the reaction conditions between 0.2 and 1.5 ° C per day.
  • the hydrogen peroxide conversion is determined at short intervals.
  • the discharge of the first reactor is worked up in a distillation column in which at least 90%, typically> 99%, of the propylene oxide formed is removed overhead.
  • the remaining bottom product is mixed with propylene and optionally with a basic salt and reacted in a second reactor (post-reactor, for example a simple tube or shaft reactor).
  • a second reactor for example a simple tube or shaft reactor.
  • the postreactor preferably 90 to 95% of the hydrogen peroxide used in this case are reacted, since at lower conversions the safety problematic hydrogen peroxide is often left over, but at higher conversions the selectivity of the reaction often drops.
  • the process control for example, the input temperature or the amount of base, according to the online determined content of hydrogen peroxide, adapted.
  • the schematic structure is in FIG. 1 shown.
  • the triggering of the UV / VIS spectrometer is preferably carried out by the process titrator. Then a transmission probe is immersed in each of the reaction vessels in the process titrators. If these transmission probes are connected via optical fibers (preferably of quartz) to an optical multi-channel multiplexer, a spectrometer is generally sufficient for the (almost) simultaneous recording of the absorption spectra at the various measuring points.
  • a few milliliters of sample are removed from the product stream by means of the dosing system and transferred to the reaction vessel located in the titrator.
  • the color reagent commercially available titanyl sulfate solution, about 5% by weight of Ti
  • a short time typically 1 min
  • a yellowish Titanylperoxo complex is then made up to a specific volume (typically 25 to 500 ml) with a solvent (eg distilled water, dilute sulfuric acid, etc.).
  • the conversion of the measured UV / VIS extinctions into H 2 O 2 concentrations takes place in the measuring and evaluation program on the computer with the aid of a. Calibration function.
  • the extinction in the absorption maximum of the titanyl peroxo complex at about 408 nm is preferably used.
  • the epoxidation of propylene with hydrogen peroxide was carried out in a 45 mm diameter, 2 m long, jacketed tubular reactor filled with about 620 g of a fresh epoxidation catalyst (titanium silicalite TS-1 in the form of 1.5 mm diameter strands). carried out.
  • the quantities used of the individual educts were as follows: methanol: 1834 g / h Hydrogen peroxide (40% in water): 332 g / h propene: 244 g / h K 2 HPO 4 solution (1.25% by weight in water): 4 g / h
  • the individual educts were combined in front of the reactor under pressure (about 20 bar) and passed through the reactor.
  • the temperature of the cooling medium in the jacket space was about 30 ° C. at the beginning of the experiment.
  • the temperature of the cooling medium was adjusted so that a constant conversion of hydrogen peroxide was achieved.
  • the hydrogen peroxide in the effluent of the reactor was determined online as described in Examples 1 and 2.
  • Fig. 3 shows a comparison between the determined with the online or offline method content of hydrogen peroxide in the reaction effluent of the reactor described in the example.
  • the online procedure is in Fig. 3 represented by a line; the offline method using circular measuring points.

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EP02722046A 2001-02-07 2002-02-05 Verfahren zur Steuerung der Oxidation von Propen mit H2O2 Expired - Lifetime EP1384064B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10105528A DE10105528A1 (de) 2001-02-07 2001-02-07 Verfahren zur Online-Bestimmung von Wasserstoffperoxid
DE10105528 2001-02-07
PCT/EP2002/001178 WO2002063285A2 (de) 2001-02-07 2002-02-05 Verfahren zur online-bestimmung von wasserstoffperoxid

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EP1384064A2 EP1384064A2 (de) 2004-01-28
EP1384064B1 true EP1384064B1 (de) 2009-12-09

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US (1) US7351587B2 (ru)
EP (1) EP1384064B1 (ru)
CN (1) CN1271060C (ru)
AT (1) ATE451614T1 (ru)
AU (1) AU2002252993A1 (ru)
BR (1) BR0207099A (ru)
CA (1) CA2437747A1 (ru)
DE (2) DE10105528A1 (ru)
MX (1) MX247272B (ru)
MY (1) MY138716A (ru)
RU (1) RU2003127407A (ru)
SA (1) SA02220667B1 (ru)
WO (1) WO2002063285A2 (ru)
ZA (1) ZA200306054B (ru)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10121194A1 (de) * 2001-04-30 2002-10-31 Basf Ag Vorrichtung zur Steuerung von chemischen Syntheseprozessen
DE10240129B4 (de) 2002-08-30 2004-11-11 Basf Ag Integriertes Verfahren zur Synthese von Propylenoxid
WO2005050183A2 (de) * 2003-11-19 2005-06-02 Nttf Gmbh Vorrichtung und verfahren zur untersuchung einer flüssigkeitsprobe
IL160989A (en) * 2004-03-21 2009-09-22 Mistral Detection Ltd Method and kit for detecting explosive substances containing certain oxidants
CN100468052C (zh) * 2007-04-13 2009-03-11 四川大学 一种过氧化氢敏感材料及其制备方法和用途
DE102008036731B3 (de) * 2008-08-07 2009-12-31 Licht, Michael, Dr. Ing. Vorrichtung und Verfahren zur optischen Bestimmung der Wasserstoffperoxidkonzentration
BR112012001033B8 (pt) * 2009-07-16 2021-03-23 Basf Se método para separar acetonitrila de água, e, processo altamente integrado para a preparação de óxido de propileno
CN102612649A (zh) * 2009-11-20 2012-07-25 犹他大学研究基金会 探测基于过氧化物的爆炸物的传感器和方法
IT1397378B1 (it) 2009-12-30 2013-01-10 Novamont Spa Processo continuo di scissione ossidativa di oli vegetali
IT1397379B1 (it) 2009-12-30 2013-01-10 Novamont Spa Processo continuo per la produzione di derivati di acidi carbossilici saturi
CN102116744B (zh) * 2010-02-08 2015-08-05 力德力诺生物技术(北京)有限公司 一种检测双氧水的检测装置的制备方法
DE102011003720A1 (de) * 2011-02-07 2012-08-09 Robert Bosch Gmbh Anordnung und Verfahren zum Detektieren von Wasserstoffperoxid
WO2013001534A1 (en) 2011-06-28 2013-01-03 Mistral Detection Ltd. A reagent method and kit for the detection of nitro aliphatic compounds
US20140193923A1 (en) * 2012-04-18 2014-07-10 University Of Utah Research Foundation Sensors and methods for detecting peroxide based explosives
TWI527762B (zh) 2013-08-15 2016-04-01 國立中山大學 金屬氧化物材鍛燒物之用途
US9835601B2 (en) 2014-05-21 2017-12-05 Spi Technology Ltd. Apparatus and method for measuring hydrogen peroxide in water
CN103713061B (zh) * 2013-12-30 2015-06-03 华南理工大学 一种通过测定氧气浓度来确定过氧化氢含量的方法
CN103837514B (zh) * 2014-03-13 2016-04-20 重庆大学 一种流动注射荧光法测定过氧化氢的装置
US11231360B2 (en) * 2017-06-29 2022-01-25 Hydrite Chemical Co. Automatic titration device
US11397171B2 (en) 2017-09-18 2022-07-26 Ecolab Usa Inc. Adaptive range flow titration systems and methods with sample conditioning
BR112020020717B1 (pt) * 2018-04-09 2023-10-24 Ecolab Usa Inc Sistema de titulação automatizado, e, método para quantificar uma concentração de analito alvo em uma corrente de amostra
US11397170B2 (en) * 2018-04-16 2022-07-26 Ecolab Usa Inc. Repetition time interval adjustment in adaptive range titration systems and methods
EP3812375A1 (en) * 2019-10-21 2021-04-28 Evonik Operations GmbH Process for the epoxidation of propene
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0068289A1 (de) * 1981-06-16 1983-01-05 Resortowy Osrodek Badawczo-Rozwojowy Automatyzacji Procesow Chemicznych "CHEMOAUTOMATYKA" Verfahren und Anordnung zur Steuerung chemischer Prozesse
EP1006100A1 (en) * 1998-12-04 2000-06-07 BP Chemicals Limited Process for the production of vinyl actetate

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4418203A (en) * 1981-12-21 1983-11-29 Shell Oil Company Process for the epoxidation of olefins
US4670385A (en) * 1984-05-21 1987-06-02 Eastman Kodak Company Compositions and elements containing triarylmethane leuco dyes and methods using same
SU1286995A1 (ru) 1984-12-20 1987-01-30 Институт Экспериментальной Метеорологии Способ определени пероксида водорода в водных растворах
US5139956A (en) * 1986-09-02 1992-08-18 Fiatron-Eppendorf, Inc. Method and system for determining peroxide content
JPS63137699A (ja) * 1986-11-28 1988-06-09 Fuji Photo Film Co Ltd 酵素活性測定用分析要素
JPS63291594A (ja) 1987-05-25 1988-11-29 Wako Pure Chem Ind Ltd 過酸化水素の定量方法
JP2516381B2 (ja) 1987-10-26 1996-07-24 第一化学薬品株式会社 過酸化水素の定量方法及びその定量用試薬
JP2954661B2 (ja) 1990-05-31 1999-09-27 協和メデックス株式会社 過酸化水素の定量法
SE9003496D0 (sv) * 1990-11-02 1990-11-02 Eka Nobel Ab Analysmetod
US5710012A (en) * 1993-08-25 1998-01-20 Actimed Laboratories, Inc. Salt of 6-carboxy-3-methylbenzothiazolone hydrazone hydrate in colorimetric determination of hydrogen peroxide
DE4425672A1 (de) * 1994-07-20 1996-01-25 Basf Ag Oxidationskatalysator, Verfahren zu seiner Herstellung und Oxidationsverfahren unter Verwendung des Oxidationskatalysators
US5646314A (en) * 1994-11-16 1997-07-08 Arco Chemical Technology, L.P. Process for titanium silicalite-catalyzed epoxidation
US5604132A (en) * 1995-01-23 1997-02-18 Olin Corporation Process flow injection analyzer and method
DE19723950A1 (de) * 1997-06-06 1998-12-10 Basf Ag Verfahren zur Oxidation einer mindestens eine C-C-Doppelbindung aufweisenden organischen Verbindung
US6037484A (en) * 1998-09-22 2000-03-14 Arco Chemical Technology, L.P. Epoxidation process
DE10121194A1 (de) 2001-04-30 2002-10-31 Basf Ag Vorrichtung zur Steuerung von chemischen Syntheseprozessen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0068289A1 (de) * 1981-06-16 1983-01-05 Resortowy Osrodek Badawczo-Rozwojowy Automatyzacji Procesow Chemicznych "CHEMOAUTOMATYKA" Verfahren und Anordnung zur Steuerung chemischer Prozesse
EP1006100A1 (en) * 1998-12-04 2000-06-07 BP Chemicals Limited Process for the production of vinyl actetate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GAUGLITZ ET AL: "Automatische digitale Erfassung zeitabhäingiger Absorptions- und Fluorescenzspektren für kinetische Messungen", ZEITSCHRIFT FÜR ANALYTISCHE CHEMIE, no. 276, 1975, pages 97 - 102 *

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EP1384064A2 (de) 2004-01-28
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CA2437747A1 (en) 2002-08-15
ZA200306054B (en) 2004-09-28
WO2002063285A2 (de) 2002-08-15
DE50214069D1 (de) 2010-01-21
SA02220667B1 (ar) 2009-02-25
BR0207099A (pt) 2004-03-02
US7351587B2 (en) 2008-04-01
AU2002252993A1 (en) 2002-08-19
MXPA03006941A (es) 2004-04-02
MY138716A (en) 2009-07-31
CN1271060C (zh) 2006-08-23
US20040048329A1 (en) 2004-03-11
ATE451614T1 (de) 2009-12-15
MX247272B (es) 2007-07-17
CN1539081A (zh) 2004-10-20
WO2002063285A3 (de) 2003-11-20

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